Aromatic diacidyl compound and process for preparing the same



' Patented Feb; 18, 1930 I.

7 UNITED STATES j PATENT o'rro WULFF ND ROBERT snnLmAYn; or MUNICH, Annywnnnnn ncxnnr, on.

nocns'r-on-rnn-mnm, GERMAN AssIeNons' o ennnnar. ANILINE wonxs. 1nd,;

on NEW YORK, N. Y., A conroRA'rIoN on DELAWARE ABOMATIG DIAGIID Y L comrounn Ann rnocnss non nnnrenme rnn shite in, Drawing. Application filed October 18,1927, iiiiileezow, ajndiii ei ifiany o tane- 2 s, 1920.

wherein X and Y stand for two hydrogen atoms or for the group HzC-CH; 3 I

and R for hydrogen or a CO-alkyl group or CO aryl group and any aromatic or aliphatic acid chloride to act upon each other in the presence of aluminium chloride, with or without the use of a diluent, and, in case the R stands for hydrogen, by subjecting the hydrocarbons vfirst to the action of an acld chloride at about 0 C. and then the action of a further quantity of an acid chloride at a temperature of about 30 C.,to 100 C. in the presence of aluminium chloride.

Diacidyl-hydrocarbons arealready per se known, for instance those'of nesitylene, anthracene, phenanthrene; however, in view of the peculiar mannerin which the aluminium quantity from the high boiling portions of the reactlon product obtalned 1n the manufacture of 5-acetyl-acenaphthene. Therefore, diacetyl-acenaphthene cannot be industrially prepared in this way. It is only by our present invention that a practical way has been found to prepare the diacetyl-acenaphthene with a good yield. a

Our new process may, for instance be carried out in such a manner that there is used as parent material either a mixture .of aluminium chloride and ready-made monoacidyl-hydrocarbon or the crude aluminiumchloride-monoketo compounds produced in the manufacture 0f monoacidyl-hydrocarbons from a hydrocarbon, an acid chlom ride and aluminiumchloride, either directly or if preferred after separating the solvent.

A third way to carry out the new process is to start from the respective hydrocarbons and to proceed in the manner set forth in the 9, following examples.

The diacidyl-hydrocarbons of-the naphthalene and acenaphthene are of considerable technical interest as being valuable intermediate products for the manufacture of vat 85 dyestufi's.

The following examples serve to illustrate our invention but they are not intended to limit it thereto, all parts being parts by weight. at,

(1) 23 grams of a-benzoylnaphthalene are mixed with 16 grams of benzoyl chloride and there are then cautiously added 15 grams of aluminium chloride at about 30 C. to 35 C. There are then added in the course of one 95 houranother quantity of 21 grams of aluminium chloride while wellstirring, during which operation the temperature is gradually raised from 45 C. to C. and finallykept for another half hour at 0. During, the 100 reaction I hydrochloric acid escapes.

efiervescence; The dark brown melt thus obtained is decomposed'w'ith water, separated from the aqueous ortion; washed first with "diluted caustic so Solution and then with products (having a melting. point of about 300 C, under 12 mm. press'ure).- I 4 v The yield of"1;5-dibenzoylnaphthalene amounts to approximately 60 per cent of the isomeric (presumably-1.8-) dibenzoylnaph- 1 thalene to about 20 f'per'cent of the theory,

(2) 26 "grams, 0 5-benzoylacenaphthene are subjected to reaction as indicated in Example 1, keeping however the temperature generally somewhat lower, finally atabout 70 C. and whiletaking care that the mass is well and vigorously stirred, because the melt tends to become 'very viscous and stiff. The

reaction may also be performed in a solution of :carbon jdisulfide. The resulting crude product, after being-decomposed with wateror the like and dried, is; purified by re-- vcrystallization from alcohol or extraction with ether, there being left; undissolveda considerable quantity of a dark-secondary condensation product. ;The 'dibenzoylacenaphthene crystallizes from-the solvent in nice crystals havinga melting point of 143.

C. From the mother liquors can be obtained a further'quantity of the roduct as well as unaltered monoketone. T e yield amounts to'about 50' per cent.-

"(3) 19,5 grams of 5-acetylacenaphthene are mixed "and; stirred with 'a small quantity of carbon disulfide and to this mixture are 7 slowly added 15 grams of aluminium chloride, 1 whereupon. the orangecolored aluminium-' Y fchloride.compound separates in the form of a, magma .a There isthenaddedby drops. in

thezcourseof about hour, while very well stirring, aconcentrated solution in carbon disulfide" of the compound obtained from 12 1 gramsof'acetyl chloride and l4 grams of alu-- i chloride, during which operation the s de begins to boil. 7 decomposed with water, thecarbon disulfide tem "erature is kept at 30 G..to 35 "C. and

muc hydrochloric acid escapes. There are then furthermore slowly added '6 grams of aluminiumichloride, theresulting dark, thick mass. isthoro'ughly stirred and finally; the tel lngierature is raised until the carbon ;di-

The product is then is blown off by meansofsteam and the product of the reaction, after it has cooled, is sep arated, washed and dried. It is then dissolved in hot alcohol and an residue left is filtered ofli. After cooling, t e diacetyl acenaphthene crystallizesin beautiful'crystals which melt at'146 C; A further quantity of. the principal substance canbe obtained from the mother liquor by concentration and a portion of unaltered 5-acetyl acenaphtheneby vacuum distillation or" by crystallization.

The'yieldof diace y 5 I i to. -80 per cent of the converted 5-acetyl-' acenaphthene.

1(4) 128 parts of'naphthalene are sus- I pended in 128 parts of benzoylchloride at 0 (land to this mixture are added by portions 200 grains of-aluminium chloride, carebeing taken that the temperature does not exceed 0 C. The mass 'is kept at a temperature of 0 C. until the evolution of hydrochloric acid has ceased; there are then again added 160 grams of .benzoyl chloride; the whole'ii's heated to 3040 'C. and at this temperature 150 grams of aluminium chloride are added in portions. When all of the aluminium chloride has been introduced, the mass isheated to C. there are again added 200 grams of aluminium chloride and the whole heated for one hour to C. The final product, after being decomposed with water and distilledby means of steam yield when recrystallized from lacial acetic 1 .5-dibenzoylnaphthalenew1th a yield of 70 per 7 cent. 7

I Into a mixture of 46 parts na ch oride in 400 parts of carbon disulfide. are

' introduced, while externally cooling, 110

parts of aluminium chloride care being taken:

of acei phthene and 99 parts of -'mono-chloracetylby cooling that the solvent does not become v heated by the reaction-heat to the boiling point. After all of the'aluminium chloride has been introduced the mass is allowed to stand fora rather long time (preferably for about 24 hours) while cooling and it is then heated for about one'hour on the steam bath.

After decomposition with ice followed by distillation with steam to remove the carbon disulfide, the residue is recrystallized from glacial acetic acid. The so obtained hitherto unknown dichloroacetylacenaphthene which has'probably the following formula: 1

' Q 4 Inc-#011,, '1 w shows the form of large almost colorless needles, melting at 194 C(to 195 C. In this manner the said compound is obtained ut 70 per cent.- v e (6) If instead of the chloracetyl chloride according to Example 5, acet l chloride is used and the operatlons carrie out with the "by a single operation and with a yield of same quantities as indicated in this example, there is obtained after purification and reprecipitation of the crude product from alcohol, the di-acetyl-acenaphthene in colorless prisms melting at 146 C.

We claim:

1. The process of preparing an aromatic diacidyl compound which comprises causing a clompound of the following general formu a:

wherein X and Y stand for hydrogen or jointly for the group I-I C-CH and R rep resents hydrogen, CO-alkyl or CO-aryl, to react with an acid chloride in the presencepf aluminium chloride.

2. The process of preparing an aromatic diacidyl compound which comprises causing a compound of the following general formula:

wherein X and Y stand for hydrogen or jointly for the group H CCH to react with an acid chloride, first with a quantity at about 0 C. and then with a further quantity at a temperature of about 30 C. to 100 C., in the presence of aluminium chloride.

3. The process of preparing an aromatic diacidyl compound which comprises causing a compound of the following general formula:

wherein X and Y stand for hydrogen or jointly for the group PFC-CH and R represents hydrogen, CO-alkyl or CO-aryl, to react with benzoyl chloride in the presence of aluminium chloride.

4. The process of preparing an aromatic diacidyl compound which comprises causing a compound of the following general formula:

wherein X and Y stand for hydrogen or jointly for the group H il-CF1 to react with benzoyl chloride, first with a quantity at about 0 C. and then with a further quantity at a temperature of about 30 to 100 (3., in the presence of aluminium chloride.

5. The process of preparing an aromatic diacidyl compound which comprises causing a compound of the following general formula mula

wherein R stands for hydrogen, CO-alkyl or CO-aryl to react with benzoyl chloride in the presence of aluminium chloride.

8. The process of preparing an aromatic diacidyl compound which comprises causing naphthalene to react w'th benzoyl chloride, first with a quantity at ipbout 0 C. and then with a further quantity at a temperature of about 30 C. to 100 0., in the presence of aluminium chloride.

In testimony whereof, we aflix our signatures.

OTTO WULFF. ROBERT SEDLMAYR. DR. WILHELM ECKERT. 

